CN100410354C - System having dlc contacting faces, method for lubricating the system and lubricating oil for the system - Google Patents

Abstract

The present invention relates to a lubricant for lubricating relatively movable, facing contact surfaces at least one of which is coated with DLC, a method of lubricating DLC contact surfaces with this lubricant, and a system having DLC contact surfaces. The lubricant fulfills the following conditions (a) and (b): (a) the lubricant contains a lubricant base oil containing, as a main component, a base oil composed at least one of a hydrocracked mineral oil, a wax-isomerized mineral oil, and a poly-+--olefin base oil. The base oil has a kinematic viscosity of 2 to 20 mm 2 /s at 100 DEG C, a total aromatic content of not higher than 5 wt%, and a sulfur content of 0.005 wt%; and (b) the lubricant has a sulfur content of not higher than 0.2 wt%.

Description

Has the system of DLC surface in contact, the method for lubricated this system and the lubricating oil that is used for this system

Technical field

The present invention relates to have a kind of system of DLC surface in contact, as oil engine, wherein as relatively movably, face-to-face surface in contact is coated with one of at least DLC.The present invention also relates to be used for a kind of lubricant of said system and a kind of method of lubricating the DLC surface in contact with this lubricant.

Background technology

Recently, the global environment problem is noticeable, as global warming and ozone-depleting.CO particularly ₂Discharge quite noticeablely, it is said that its remarkably influenced the earth and warm, and each state all pays close attention to its required standard.

CO ₂One of main challenge that reduces is to reduce the energy waste that the friction waste causes in machinery, the system etc., especially will reduce vehicle fuel consumption.In reducing engine etc., have relatively movably, face-to-face aspect the friction of surface in contact parts, as sliding surface, rotating surface or rolling surface, form the material of this surface in contact and lubricant that this surface in contact with every kind of material system is lubricated plays an important role.

Concerning middle parts such as engine, under serious friction waste condition, the material that forms this surface in contact must have fabulous abrasion resistant qualities and low frictional factor.In order to reach these purposes, people have used various hard film materials recently.For example, compare with CrN with hard coating of abrasion resisting such as TiN, do not having under the situation of lubricant, the DLC material is confirmed as a kind of low abrasives because of its coefficient of friction in air is low.

In order to reduce power loss in the lubricant, for example, in order to improve the motor spirit loss, proposed to reduce the resistance of agitating in viscous resistance in the hydrodynamical lubrication zone and the engine by the viscosity that reduces lubricant, and by add the suitableeest friction modifier and various additive reduce mix with the boundary regions of lubrication in the friction waste.Broad research should the friction modifier, developed organic molybdenum such as dithiocarbonic acid molybdenum (MoDTC) and molybdenum dithiophosphate (MoDTP) especially, and the lubricant that contains organic molybdenum, and obtained effect; Operational phase shows fabulous low frictional factor at the ordinary steel sliding surface in the early stage.

On the other hand, existing report, the DLC material that has fabulous low friction characteristics in air is having under the situation of lubricant, only has limited friction and reduces effect (non-patent literature publication 1); Report is also arranged, and the lubricant that contains a kind of organic molybdenum is used for the DLC material and can produce enough friction reduction effects (non-patent literature publication 2).

Non-patent literature publication 1: Japan friction scholar understands communique (Japanese Society ofTribologists, Congress Proceeding), Tokyo, 1999.5, the 11-12 pages or leaves, Kano etc.

Non-patent literature publication 2: world's friction association communique (World Tribology Congress, Proceeding) 2001.9, vienna, the 342nd page, Kano etc.

Summary of the invention

An object of the present invention is to provide a kind of system of the DLC of having surface in contact, the friction that is coated with wherein relatively movably, one of at least between the face-to-face surface in contact of DLC further reduces, and stablely keeps this low friction characteristics.

Another object of the present invention provides a kind of lubricant that is used to have DLC surface in contact system, and it is applicable to that further reduction is coated with the friction between the face-to-face surface in contact of DLC relatively movably, one of at least, and stablely keeps low friction characteristics.

A further object of the present invention provides a kind of method of lubricated DLC surface in contact, and it can further reduce relatively movably, be coated with one of at least the friction between the face-to-face surface in contact of DLC, and the lubricated stable surface in contact that keeps low friction characteristics.

According to the present invention, the system with DLC surface in contact is provided, comprising:

Relatively movably, be coated with one of at least DLC face-to-face surface in contact and

Be used for having a kind of lubricant of the system of DLC surface in contact, this lubricant is dispersed between the described contact surface; Described lubricant comprises a kind of lubricating base oil (A), and this a kind of lubricating base oil (A) contains a kind of base oil as principal constituent (X); This base oil (X) is formed and is comprised the mineral oil of at least a hydrocracking, the isomerized mineral oil of a kind of wax and a kind of many α thiazolinyl oil; Kinetic viscosity was 2-20mm when wherein said base oil (X) had 100 ℃ ²/ s, total aromatic content is not higher than quality 5%, and sulphur content is not higher than quality 0.005%.

According to the present invention, a kind of lubricant that is used for having the system of DLC surface in contact also is provided, described lubricant is used for the lubricated face-to-face surface in contact that is coated with DLC relatively movably, one of at least, and described lubricant comprises:

A kind of lubricating base oil (A) contains a kind of base oil (X) as principal constituent; This base oil (X) is formed and is comprised the mineral oil of at least a hydrocracking, the isomerized mineral oil of a kind of wax and a kind of many α thiazolinyl oil; Kinetic viscosity was 2-20mm when wherein said base oil (X) had 100 ℃ ²/ s, total aromatic content is not higher than quality 5%, and sulphur content is not higher than quality 0.005%.

According to the present invention, a kind of method of lubricated DLC surface in contact also is provided, comprise and use above-mentioned lubricant, be dispersed between the contact surface of system the lubricated face-to-face surface in contact that is coated with DLC relatively movably, one of at least with DLC surface in contact.

Lubricant of the present invention is lubricated relatively movably with low friction level, be coated with one of at least the face-to-face surface in contact of DLC, as sliding surface, rotating surface, rolling surface etc., also stablely keeps this low friction characteristics.This system and method in addition,, uses above-mentioned lubricant of the present invention, so that can provide extensively energy-conservation having various mechanical fields and the system that DLC coatingsurface and requirement have low friction characteristics according to system of the present invention and lubricating method.

According to lubricant of the present invention, system and lubricating method, can be not limited to and be used for various machineries and have relative removable, the face-to-face surface in contact of device of low friction characteristics, and can provide extensively energy-conservation in various fields with requiring.In addition, according to lubricant of the present invention, be not only applicable to have relatively movably, be coated with one of at least the various machineries and the system of the face-to-face surface in contact of DLC, and adopt the various machineries and the system of this surface in contact applicable to wherein the sliding surface parts or the basic element of character, to reduce the friction waste of whole machinery and system.

Brief Description Of Drawings

Fig. 1 is the test block view that preparation is used on SRV friction experiment machine among the embodiment.

Preferred forms

Now introduce the present invention in detail.

System of the present invention has relatively movably, be coated with one of at least the face-to-face surface in contact of DLC.This surface in contact can be to have on a surface that is coated with DLC and its to scribble or do not scribble the metal of a kind of material that is not that DLC films or another surface of non-metallic material system, and perhaps, two surface in contacts all are coated with DLC.

Relatively movably, one of at least, the face-to-face surface in contact that is coated with DLC comprises sliding surface, rotating surface, rolling surface etc., and wherein one of surface in contact or both move and produce the relative movement on surface face-to-face.

The DLC material that forms this DLC film coated surface is that a kind of carbon is the invisible material of major constituent, and, at diamond lattic structure (SP ³Bond structure) and graphite key (SP ²Key) includes carbon bond in.Especially the DLC material can be the a-C (invisible carbon) that only is made up of carbon, the a-C:H (the invisible carbon of hydrogenation) that contains hydrogen, or has the MeC (metallic carbide) of metallic element such as titanium (Ti) or molybdenum (Mo).The preferred surface in contact of the present invention has at least one surface and scribbles a kind of a-C sill and do not have hydrogen as the DLC material, because it has remarkable reduction friction effect.

The body material that formation is coated with the DLC surface does not have particular determination, preferably uses iron, and this DLC coated surface can adopt conventional PVD or CVD method.

In the surface in contact, one is the DLC coated surface, and another is not the DLC film coated surface; Form the body material of DLC coated surface and form this another surperficial material and do not have particular restriction.Howsoever, can use a kind of metal, as iron-based, aluminium base, manganese base or titanium base material, preferred especially iron-based, aluminium base and manganese sill, because these materials in existing machinery and system relative movably, the conventional use in the surface in contact face-to-face, and, in every field, be widely used in energy-conservation.Produce this another surface etc. and also can use non-metallic material, as resin, plastics or carbon.Except DLC, can be with the surface that metal or non-metallic material form with a kind of various films of material, as TiN or CrN.Preferred this film forms on the matrix of metallic substance such as iron-based, aluminium base, manganese base or titanium base material system.

Iron does not have particular determination, not only can use puron, can use various ferrous alloys yet, wherein with iron arbitrarily bonded can be carbon, nickel, copper, zinc, chlorine, cobalt, molybdenum, lead, silicon, titanium or wherein two kinds or multiple.The exemplary embodiments of this iron can comprise carbon steel SCM420 and SCr420 (JIS).

Alumina-base material does not have particular determination, not only can use raffinal, can use various aluminum base alloys yet.For example, preferably contain the hypoeutectic or the super eutectic aluminum alloy of quality 4-20% silicon (Si) and quality 1.0-5.0% copper (Cu), these aluminium alloy preferred embodiments can comprise AC2A, AC8A, ADC12 and ADC14 (JIS).

The manganese sill for example can be manganese-aluminium-zinc-base (Mg-Al-Zn), manganese-aluminium-rare-earth metal matrix (Mg-Al-REM), manganese-aluminium-calcium base (Mg-Al-Ca), manganese-zinc-aluminium-calcium base (Mg-Zn-Al-Ca), manganese-aluminium-calcium-rare-earth based (Mg-Al-Ca-REM), manganese-aluminium-strontium base (Mg-Al-Sr), manganese-aluminium-silica-based (Mg-Al-Si), manganese-rare earth metal zinc-base (Mg-REM-Zn), manganese-Yin rare-earth based (Mg-Ag-REM), manganese-yttrium-rare-earth based (Mg-Y-REM) material, the any bonded material of perhaps a kind of these materials especially can use AZ91, AE42, AX51, AXJ, ZAX85, AXE522, AJ52, AS21, QS22, WE43 (ASTM).

The surface roughness of this surface in contact (Ra) can be measured according to JIS B 0601-1994, for the stability of motion of surface in contact, can be no more than 0.1um usually, preferably is no more than 0.08um.If Ra surpasses 0.1um, the concentrated wear meeting significantly increases coefficient of friction.

DLC coated surface or the surface that applies with a kind of thin-film material without DLC applies, the Vickers microhardness of preferred surface hardness is Hv1000 to 3500 (10g load), and film thickness is 0.3-2.0um.If the surface hardness Hv of film such as DLC coated surface is less than 1000, if perhaps film thickness is less than 0.3um, this coating is easy to wear away; And if if this surface hardness Hv surpass 3500 or film thickness greater than 2.0um, this coating is easy to peel off.

When iron was used to form the matrix of another surface in contact that does not have the DLC coated surface, the Rockwell hardness C scale of preferred surface hardness was HRC45 to 60.As the representative observation cam follow-up part, its advantage be in addition the contact movement under being about the high surface stress conditions of 700Mpa in also can keep the wearing quality of face-to-face DLC coated surface.If the surface hardness of iron is less than HRC45, the DLC film coated surface is understood easily deformable or is peeled off face-to-face under high surface pressure.

When alumina-base material is used to form the matrix of another surface in contact that does not have the DLC coated surface, the Brinell hardness H of preferred surface hardness _BBe 80-130.If the surface hardness of alumina-base material is less than H _B80, the surface of alumina-base material can be easy to wearing and tearing.

When the manganese sill is used to form the matrix of another surface in contact that does not have the DLC coated surface, the Brinell hardness H of preferred surface hardness _BBe 45-95.If the surface hardness of manganese sill is less than H _B45, the surface of manganese sill can be easy to wearing and tearing.

The lubricant that is used for system of the present invention can be the lubricant in the system according to the invention.

According to lubricant of the present invention, comprise lubricating base oil (A), this lubricating base oil contains the base oil (X) of specialized character as principal constituent, have one or more hydrocracking mineral oil, a kind of wax isomerization mineral oil and a kind of many α thiazolinyl oil in the composition of this base oil, preferably this lubricating oil does not contain zinc dithiophosphate and/or a kind of sulfur-bearing metal brightener.

The hydrocracking mineral oil that is used for base oil (X) does not have particular determination, as long as this oil has the proterties of discussing later, and it is just passable to adopt ordinary method to produce.

The wax isomerization mineral oil that is used for base oil (X) does not have particular determination, as long as this oil has the proterties of discussing later, and can enrich isomery wax from the routine paraffin wax that the lubricant dewaxing process obtains and produce, wax bits or GTL (gas is to the liquid) wax that obtains from Fischer-Tropsch reaction are with ordinary method formation isomery paraffin.Isomery wax mineral oil also can select step as distilling, producing with solvent extraction, solvent dewaxing, Hydrodewaxing and hydrogenation refining by suitable combination.

The many α thiazolinyl oil that is used for base oil (X) can be polymkeric substance or the multipolymer of C2-C30, many α thiazolinyl oil or its hydride of preferred C8-C16.Preferred especially many α thiazolinyl oil that uses is as 1-octene or 1-decene oligomer or its hydride.

The kinematic viscosity of base oil (X) is 2-20mm at 100 ℃ ²/ s, preferred 3-10mm ²/ s, more preferably 3.5-5mm ²/ s.The kinematic viscosity of base oil (X) is 2mm when setting 100 ℃ ²/ s or higher, the lubricant that can obtain can form the oil film of capacity, has fabulous oilness, and this base oil vaporization losses is lower under the mal-condition.The kinematic viscosity of base oil (X) is to 20mm when setting 100 ℃ ²/ s or lower, liquid resistance can be too not high when stirring to make base oil, and can obtain the effect of lubricant at the low frictional resistance of oiling point performance.

Total aromatic series amount in the base oil (X) is not higher than 5% of quality, preferably is not higher than 3% of quality, the more preferably 0-2% of quality.Reduce the low friction that total aromatic series amount is more conducive to realize and keep the DLC film coated surface.

Here used total aromatic series amount is meant the aromatic series amount part of measuring according to ASTMD2549.Aromatic series partly generally includes: alkylbenzene, alkylnaphthalene, anthracene, phenanthrene and alkylate thereof; The compound that four or a plurality of phenyl ring condensation produce; The compound such as pyrimidine, quinoline, phenol or the naphthols that perhaps have hetero-aromatic ring.Sulfur content in the base oil (X) is not higher than 0.005% of quality, preferably is not higher than 0.002% of quality, most preferably sulfur-bearing not substantially in the base oil (X).Also more help obtaining and keeping the lower friction of DLC film coated surface by the sulfur content that reduces in the base oil (X).

The viscosity of base oil (X) is not particularly limited, and is not less than 80 usually, preferably is not less than 100, more preferably is not less than 120, most preferably is not less than 125.The upper limit of viscosity index is generally 200-300.Selection has the base oil (X) of high viscosity index (HVI), and lubricant not only can have fabulous viscosity characteristics at low temperature, and can obtain the effect that superpower friction reduces.

Lubricant base oil (A) preferably only contains base oil (X), but can suitably contain a small amount of other base oil, only otherwise remarkably influenced effect of the present invention, for example, be no more than 30% of lubricant base oil (A) total amount quality, preferably be no more than 20% of quality, more preferably no more than 10% of quality.

Another kind of base oil can be the mineral oil that does not possess above-mentioned characteristic, the winterized stearin that obtains under appropriate condition, the synthetic wet goods except many α thiazolinyl oil.The example that does not possess the mineral oil of above-mentioned characteristic can comprise solvent extraction oil and solvent dewaxed oil.Synthetic oil example except many α thiazolinyl oil can comprise: alkylnaphthalene; Alkylbenzene; Diester such as double tridecyl penta diester, the own diester of two octyl, the own diester of two isodecyl alkyl, the own diester of double tridecyl and two octyl diester in the last of the ten Heavenly stems; Multi-hydroxy ester such as trimethylolpropane caprylate, TriMethylolPropane(TMP) pelargonate, tetramethylolmethane-2-ethylhexanoate and tetramethylolmethane pelargonate with and two or more mixture.

As long as effect of the present invention does not reduce or in order to improve effect of the present invention and other effect, except lubricating base oil (A), lubricant of the present invention can select to contain additive, for example can select a kind of no sulfur metal stain remover (B), a kind of no sulphur phosphate cpd (C), the ashless antioxidant of a kind of no sulphur (D) and two or more mixture wherein.

Component (B) can be as basic metal or alkaline-earth metal salicylate, the carbonate of basic metal or alkaline-earth metal phenates (do not have sulfur-crosslinked and be limited to these are crosslinked as use thiazolinyl) or basic metal or alkaline-earth metal.Basic metal can be sodium, potassium etc., and alkaline-earth metal can be calcium, manganese, barium etc.Metal preferred bases earth metals, especially calcium in the metal brightener.

Component (B) can be neutral, alkaline or peralkaline and can use wherein any.Particularly neutral alkaline-earth metal salicylate has good friction and reduces effect.Alkaline or peralkaline metal brightener can be as containing a kind of metal brightener of lime carbonate and/or lime borate, also can use wherein any.But the alkaline-earth metal salicylate that contains lime borate particularly contains lime borate and alkaline-earth metal salicylate not calciferous, and is preferred especially because its fabulous actual friction reduces effect.

The total alkali radix order of component (B) does not have special qualification, is generally 10-400mgKOH/g, preferred 60-350mgKOH/g.Preferably use one or both components (B) to be 60-150mgKOH/g and 150-350mgKOH/g.

In a word, when lubricants degrade forms mud shape body etc., destroy the lubricating condition of DLC surface in contact, friction is tended to increase.But the adding that it has been generally acknowledged that component (B) is scattered in the oil mud shape body that produces in the lubricant etc., and it stops lubricating condition to be degenerated, and keeps friction to reduce effect.In addition, component (B) also stops the impaired degeneration of lubricant, and the result keeps friction to reduce effect.

Therefore, improve this effect for further, and improve soil release characteristics, preferably add component (B).If have, the content of component (B) does not have particular determination.When being used for oil engine, in order to reduce the sulphiting ash content, the content of metallic element item is preferably the 0.01-1 quality % of lubricant total amount, and more preferably 0.05-0.3 quality % is most preferably not exceeding 0.2 quality %.

As long as not obvious reduction effect of the present invention, lubricant of the present invention can also select the little metal stain remover except component (B).

Component (C) is a kind of no sulphur phosphate cpd, is a kind of phosphate cpd that does not have sulphur in its molecule.The example of this compound can comprise phosphate cpd such as phosphorous acid monoesters, phosphorous acid diester, tris phosphite, phosphate monoester, phosphodiester and the phosphotriester of no sulphur, the alkyl that each all contains C1-C30, comprise its metal-salt with and amine salt.

The C1-C30 alkyl can be preferred: straight or branched C1-C30 alkyl, straight or branched C1-C30 thiazolinyl, C5-C13 cycloalkyl or straight or branched alkyl-cycloalkyl, C6-C18 aryl or straight or branched alkaryl, perhaps C7-C19 aralkyl.Alkyl or aryl can be one of elementary, secondary or three grades.

C1-C30 alkyl exemplary can comprise: alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl; Thiazolinyl such as propenyl, pseudoallyl, butenyl, butadienyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, hendecene base, laurylene base, tridecylene base, tetradecene base, ten pentaene bases, hexadecylene base, 17 thiazolinyls, octadecylene base such as oil base, 19 thiazolinyls, icosa alkene base, two hendecene bases, docosene base, tricosene base, two tetradecene bases; Cycloalkyl such as cyclopentyl, cyclohexyl, suberyl; Alkyl-cycloalkyl such as methylcyclopentyl, dimethylcyclopentyl, the ethyl cyclopentyl, the propyl group cyclopentyl, the ethyl-methyl cyclopentyl, the trimethylammonium cyclopentyl, the diethyl cyclopentyl, the ethyl dimethylcyclopentyl, the propyl group methylcyclopentyl, propyl group ethyl cyclopentyl, the dipropyl cyclopentyl, propyl group ethyl-methyl cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, the ethyl cyclohexyl, the propyl group cyclohexyl, the ethyl-methyl cyclohexyl, trimethylcyclohexyl, the diethyl cyclohexyl, the ethyl Dimethylcyclohexyl, the propyl group methylcyclohexyl, propyl group ethyl cyclohexyl, the dipropyl cyclohexyl, propyl group ethyl-methyl cyclohexyl, the methyl suberyl, the dimethyl suberyl, the ethyl suberyl, the propyl group suberyl, the ethyl-methyl suberyl, the trimethylammonium suberyl, the diethyl suberyl, ethyl dimethyl suberyl, propyl group methyl suberyl, propyl group ethyl suberyl, the dipropyl suberyl, propyl group ethyl-methyl suberyl; Aryl such as phenyl and naphthyl; Alkaryl such as tolyl, xylyl, ethylbenzene base, propyl phenyl, second tolyl, trimethylphenyl, butylbenzene base, third tolyl, diethyl phenyl, second xylyl, tetramethylphenyl, penta phenyl, own phenyl, heptan phenyl, hot phenyl, nonyl phenyl, the last of the ten Heavenly stems phenyl, 11 phenyl and ten phenylbenzene; Aralkyl such as benzyl, methyl-benzyl, dimethyl benzyl, styroyl, methylbenzene ethyl and dimethyl benzene ethyl.

Alkyl comprises the straight or branched structure that all can be expected, and it all is arbitrarily that the position of double bond in the thiazolinyl, alkyl are attached to the position of cycloalkyl, the position that alkyl is attached to aryl, the position that aryl is attached to alkyl.In addition, alkyl can have (gathering) olefin oxide, as (gathering) ethylene oxide or (gathering) propylene oxide.

The preferred example of component (C) can comprise phosphorous acid monoesters, phosphorous acid diester, tris phosphite, phosphate monoester, phosphodiester and phosphotriester, each has one-level, secondary or three grades of alkyl and metal-salt and its amine salt of C3-C24, preferred C4-C18, more preferably C4-C12.Wherein, preferably phosphoric acid ester and metal-salt thereof and its amine salt, the metal-salt and the amine salt (amine compound) of special preferably phosphoric acid monoesters and/or phosphodiester.

Metal in the metal-salt does not have special qualification, for example, can be: a kind of basic metal, as lithium, sodium, potassium or caesium; A kind of alkaline-earth metal is as calcium, manganese or barium; A perhaps heavy metal species is as zinc, copper, iron, lead, nickel, silver, magnesium or molybdenum.Wherein preferred bases earth metals such as calcium, magnesium and zinc, more preferably zinc.

Amine in the amine salt does not have particular determination, for example, can be ammonia, monoamine, diamines or polyamines.Typical example comprises: have the alkylamine of C1-C30 alkyl, as methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, undecylamine, amino dodecane, tridecyl amine, tetradecy lamine, pentadecyl amine, cetylamine, heptadecyl-amine, stearylamine, dimethyl amine, diethylamide, dipropylamine, dibutylamine, diamyl amine, dihexyl amine, diheptyl amine, dioctylamine, dinonyl amine, didecylamine, two undecyl amine, two lauryl amines, di(tridecyl)amine, two tetradecylamines, two pentadecyl amine, double hexadecyl amine, two heptadecyl amine, dioctadecylamine, methylethyl amine, methyl-propyl amine, methyl butyl amine, ethyl propyl amine, N-Ethylbutylamine, the propyl group butylamine; Enamine with C2-C30 thiazolinyl (straight or branched) is as vinyl-amine, allylamine, butenylamine, octene amine and oleyl amine; Alkanolamine with C1-C30 chain triacontanol base (straight or branched) is as carbinolamine, thanomin, Propanolamine, butanolamine, amylalcohol amine, hexanol amine, enanthol amine, octanol amine, nonyl alcohol amine, methanol amine, methyl alcohol Propanolamine, methyl alcohol butanolamine, ethanol propanol amine, ethanol and butanol amine, propyl alcohol butanolamine; Alkylenediamine with C1-C30 alkylidene group is as methylene diamine, ethylene diamine, trimethylene diamine, butylene diamine; Polyamines such as diethylenetriamine, Triethylenetetramine (TETA), tetracthylene pentamine and five ethylidene hexylamines; The heterogeneous ring compound that comprises above-mentioned monoamine with C8-C20 alkyl or alkenyl, diamine, polyamine is as undecane diethylamide, undecane diethanolamine, dodecane dipropanolamine, oil base diethanolamine, oil base propylidene diamines and stearyl tetracthylene pentamine and N-hydroxyethyl oil-based imidazoline; And alkylene oxide adduct; Its mixture and compound such as alkyl or alkenyl succinic diamide.

In these amine compound, preferably has the fatty amine (straight or branched) of C10-C20 alkyl or alkenyl, as decyl amine, lauryl amine, tridecyl amine, heptadecyl amine, octadecylamine, oleyl amine and stearylamide.

Can think that the lubricating condition deterioration that the degradation products that component of the present invention (C) inhibition produces because of lubricants degrade causes stops friction to increase, and more helps keeping the low friction characteristics of lubricant.Therefore, in order further to improve this effect and to improve abrasion resistant qualities, preferably comprise component (C).The content of component (C) is not particularly limited, and is generally the 0.1-5 quality % of lubricant total amount.When lubricant of the present invention will be used for oil engine, owing to influence exhaust after treatment system, according to phosphoric, component (C) content can be the 0.01-0.1 quality % of lubricant total amount, preferably is not higher than quality 0.08%, preferably preferably is no more than 0.06% of quality.

Component (D) is that a kind of no sulphur does not have the ash content antioxidant, is the no ash content polyphenoils that does not have sulphur atom in its molecule, for example can be the sulfurless benzene phenolic antioxidant or does not have the thiamines antioxidant.Use sulfur-bearing not have the ash content antioxidant and can movably produce negatively influencing between one of them face-to-face surface in contact at least relative with the DLC coating, and to keeping low friction that negative interaction is arranged.

The sulfurless benzene phenolic antioxidant can comprise as the example of component (D): 4,4 ' methylene-bis (2,6-pair-tert-butyl phenol), 4,4 ' two (2,6-pair-tert-butyl phenol), 4,4 '-two (2-methyl-6-tert-butylphenols), 2,2 ' methylene-bis (4-ethyl-6-tert-butyl phenol), 2,2 ' methylene-bis (4-methyl-6-tert-butylphenol), 4,4 ' butylidene two (3-methyl-6-tert-butylphenol), 4,4 ' isopropylidene two (2,6-pair-tert-butyl phenol), 2,2 '-methylene-bis (4-methyl-nonylphenol), 2,2 '-isobutylene two (4, the 6-xylenol), 2,2 ' methylene-bis (4-methyl-6-hexamethylene phenol), 2,6-pair-tert-butyl-4-methylphenol, 2,6-pair-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butyl phenol, 2,6-pair-uncle-alpha-alpha-dimethyl acid amides-p-Cresol, 2,6-pair-tert-butyl-4 (N, N '-dimethylaminomethyl phenol), tridecyl-3-(3,5-pair-tert-butyl-4-oxybenzene) propionic ester, [3-(3 for Ji Wusi alkane-quadruple, 5-pair-tert-butyl-4-hydroxyphenyl) propionic ester, octyl group-3-(3,5-pair-tert-butyl-4-hydroxyphenyl) propionic ester, octadecyl-3-(3,5-pair-tert-butyl-4-hydroxyphenyl) propionic ester and 3-methyl-5-tert-butyl-4-hydroxyphenyl replace aliphatic ester.Can use two or more mixtures of these materials.

No thiamines antioxidant can comprise phenyl-αNai An, alkyl phenyl-αNai An and dialkyl diphenylamine as the example of component (D).Can use two or more mixtures of these materials.

Phenol antioxidant and amine antioxidant can be used in combination.

Can think that component (D) can suppress because of lubricants degrade produces the lubricating condition deterioration that mud shape thing etc. causes, and stops friction to increase, so component (D) has the friction that improves lubricant to reduce the effect of preserving property.Therefore, in order further to improve this effect and to improve oxidative stability, preferably comprise component (D).If component (D) is arranged, the content of component (D) is the 0.01-5 quality % of lubricant total amount usually, preferred 0.1-3 quality %, more preferably 0.5-2 quality %.

Lubricant of the present invention can select to comprise a kind of friction modifier.For example, the friction modifier can be a kind of oxygen-containing organic compound or amine.And, preferably be C1-C40 ester class, amine, amides, alcohols, ethers, carboxylic-acid, ketone, aldehyde and one of carbonate and derivative thereof at least.Wherein, two or more mixture of preferred C3-C30 a kind of or its, more preferably C3-C20 aliphatic ester, aliphatics amine, aliphatic amide type, aliphatics alcohols and aliphatic carboxylic acid class and derivatives class thereof.

As long as have oxygen in its molecule, oxygen-containing organic compound can be any organic compound, can be a kind of compound that its molecule is made up of carbon, hydrogen and oxygen, perhaps in its molecule except these elements, also contain a kind of compound of halogen such as fluorine or chlorine, nitrogen, sulphur, phosphorus, boron, metal etc.

The example of oxygen containing organic compound can comprise the compound that has one of hydroxyl, carboxyl, carbonyl, ehter bond and ester bond and derivative thereof at least.Wherein, preferred compound is the oxygen-containing organic compound that has one of hydroxyl, carboxyl, carbonyl and ester bond and derivative thereof at least, the oxygen-containing organic compound that more preferably has one of hydroxyl, carboxyl and ester bond and derivative thereof at least, most preferred compound are to contain the oxygen-containing organic compound of hydroxyl and one of carboxyl and derivative thereof at least.Especially especially preferably the oxygen-containing organic compound that has hydroxyl and derivative thereof is because they have the ability that rubs between further reduction DLC surface in contact.Preferred these compounds have two or more hydroxyls.Contain a small amount of sulphur or do not have sulphur in the also preferred oxygen-containing organic compound.

The representational compound of forming by carbon, hydrogen and oxygen of said derivative and a kind of a kind of compound that obtains as nitrogenous compound, P contained compound, sulphur, sulfocompound, boron-containing compound, halogen, halogen contained compound, metal, a kind of inorganic or containing metal organic compound or alkylene oxide reaction.

The example of oxygen-containing organic compound can comprise oxygenatedchemicals such as alcohols, carboxylic-acid, ester class, ethers, ketone, aldehydes and carbonate, and these compounds also have a hydroxyl, carboxyl, carbonyl and combine an ester bond and derivative thereof and its two or more mixtures with it one of at least.

For example, alcohol can be MHA, dihydroxy alcohol, trihydroxy-alcohol or higher hydroxyl alcohol, perhaps its two or more mixture.

Has a hydroxyl in its molecule of MHA, for example can be: monohydroxy alkyl alcohol with C1-C40 of a straight or branched alkyl, monohydroxy alkenyl alcohol with C2-C40 of the straight or branched thiazolinyl that two keys are arranged in an optional position, has a straight or branched alkyl and at the alkyl of an optional position and monohydroxy (alkyl) cycloalkyl alcohol of the substituted C3-C40 of hydroxyl, has a straight or branched alkyl and at the alkyl and hydroxyl substituted (alkyl) aryl alcohol of an optional position, 6-(4-oxygen-3,5-pair-the tert-butyl anilino)-2, two (octylsulfo)-1 of 4-, 3,5-triazine, perhaps its two or more mixture.

The monohydroxy alkyl alcohol can comprise: methyl alcohol; Ethanol; Propyl alcohol such as 1-propyl alcohol and 2-propyl alcohol; Butanols such as 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol and 2-methyl-2-propyl alcohol; Amylalcohol such as 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl-2-butanols, 2-methyl-2-butanols and 2,2-dimethyl-1-propyl alcohol; Hexanol such as 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 3-methyl-3-amylalcohol, 4-methyl-1-pentene alcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 2,3-dimethyl-2-butanols, 3,3-dimethyl-1-butanols, 3,3-dimethyl-2-butanols, 2-ethyl-1-butanols and 2, the 2-dimethyl butyrate alcohol; Enanthol such as 1-enanthol, 2-enanthol, 3-enanthol, 2-methyl isophthalic acid-hexanol, 2-methyl isophthalic acid-hexanol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 5-methyl-2-hexanol, 3-ethyl-3-amylalcohol, 2,2-dimethyl-3-amylalcohol, 2,3-dimethyl-3-amylalcohol, 2,4-dimethyl-3-amylalcohol, 4,4-dimethyl-2-amylalcohol, 3-methyl isophthalic acid-hexanol, 4-methyl isophthalic acid-hexanol, 5-methyl isophthalic acid-hexanol and 2-ethylpentanol; Octanol such as 1-octanol, sec-n-octyl alcohol, 3-octanol, 4-methyl-3-enanthol, 6-methyl-2-enanthol, 2-ethyl-1-hexanol, 2-propyl group-1-amylalcohol, 2,4,4-trimethylammonium-1-amylalcohol, 3,5-dimethyl-1-hexanol, 2-methyl isophthalic acid-enanthol and 2,2-dimethyl hexanol; Nonyl alcohol such as 1 nonyl alcohol, 2-nonyl alcohol, 3,5,5-trimethylammonium-1-hexanol, 2,6-2,6-dimethyl-4-heptanol, 3-ethyl-2,2-dimethyl-3-amylalcohol, 5-methyl octanol; Decyl alcohol such as 1-decanol, 2-decyl alcohol, 4-decyl alcohol, 3,7-dimethyl-1-octanol, 2,4,6-trimethylammonium enanthol; Undecyl alcohol; Dodecyl alcohol; Tridecyl alcohol; Myristyl alcohol; Pentadecyl alcohol; Hexadecyl alcohol; Heptadecyl alcohol; Stearyl alcohol such as stearyl alcohol; Nonadecyl alcohol; Eicosyl alcohol; Heneicosyl alcohol; The tricosyl alkanol; Tetracosyl alcohol.

The example of monohydroxy alkenyl alcohol can comprise: vinyl alcohol, vinylcarbinol, butenol, hexenol, octenol, decenol, laurylene base alcohol or octadecylene base alcohol are as oleyl alcohol.

The example of monohydroxy (alkyl) cycloalkyl alcohol can comprise: cyclopentanol, hexalin, suberyl alcohol, methylcyclopentanol, methyl-cyclohexanol, butyl hexalin, dimethyl cyclohexanol, cyclopentyl carbinol, hexahydrobenzyl alcohol, cyclohexyl ethyl alcohol such as 1-cyclohexyl ethyl alcohol and 2-cyclohexyl ethyl alcohol, cyclohexyl propyl alcohol such as 3-cyclohexyl propyl alcohol, cyclohexyl butanols such as 4-cyclohexyl butanols, butyl hexalin and 3,3,5,5-tetramethyl-ring hexanol.

The example of (alkyl) aryl alcohol can comprise: phenyl alcohol, aminomethyl phenyl alcohol is as o-phenyl phenol, between phenol and Pyrogentisinic Acid, methoxycresol, ethylphenyl alcohol, propyl group phenyl alcohol, butyl phenyl alcohol, butyl methyl phenyl alcohol is as 3-methyl-6-tert-butyl phenyl alcohol, 3,5-dimethylphenyl alcohol, diethyl phenyl alcohol, dibutyl phenyl alcohol as 2,6-pair-tert-butyl phenyl pure and mild 2,4-pair-tert-butyl phenyl alcohol, dibutylmethyl phenyl alcohol as 2,6-pair-tert-butyl-4-aminomethyl phenyl alcohol, dibutyl ethylphenyl alcohol as 2,6-pair-tert-butyl-4-ethylphenyl alcohol, tributyl phenyl alcohol as 2,4,6-three-tert-butyl-4-butyl phenyl alcohol, naphthalene alcohol is as the pure and mild β of α-naphthalene-naphthalene alcohol and dibutyl naphthalene alcohol as 2,4-pair-tert-butyl-α naphthalene alcohol.

Even under hot conditions, friction reduces and reduce effect in order to guarantee low volatility and to obtain friction in order to strengthen between the DLC surface in contact, and for example, in engine, MHA is straight or branched C12-C18 alkyl alcohol preferably, as oleyl alcohol or stearyl alcohol.

Dihydroxy alcohol has two hydroxyls in its molecule, for example can be: have a straight or branched alkyl or alkenyl and at the C2-C40 alkyl or alkenyl glycol of the two keys of an optional position band thiazolinyl; Has cycloalkanes glycol at (alkyl) straight or branched alkyl of an optional position substituted alkyl and hydroxyl; Has C2-C40 dihydroxyl (alkyl) aryl alcohol at a straight or branched alkyl of an optional position substituted alkyl and hydroxyl; The condenses of right-tert-butyl phenol and formaldehyde; The condenses of right-tert-butyl phenol and acetaldehyde with and two or more mixture.

Alkyl-or the example of thiazolinyl-glycol can comprise: the ethene dibasic alcohol, the divinyl dibasic alcohol, the polyethylene dibasic alcohol, the propylene dibasic alcohol, two propylene dibasic alcohol, the polypropylene dibasic alcohol, neopentyl alcohol, 1, ammediol, 1, the 4-butyleneglycol, 1, the 2-butyleneglycol, the 2-methyl isophthalic acid, ammediol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 2-ethyl-2-methyl isophthalic acid, ammediol, 2-methyl-2, the 4-pentanediol, 1, the 7-heptanediol, 2-methyl-2-propyl group-1, ammediol, 2,2-diethyl-1, ammediol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, 2-butyl-2-ethyl-1, ammediol, decamethylene-glycol, 1,11-hendecene glycol, 1,12-laurylene glycol, 1,13-tridecylene glycol, 1,14-tetradecene glycol, 1,15-ten pentaene glycol, 1,16-hexadecylene glycol, 1,17-17 enediols, 1,18-octadecylene glycol, 1,19-19 enediols and 1,20-icosa alkene glycol.

The example of (alkyl) cycloalkyl glycol can comprise cyclohexane diol and methylcyclohexane glycol.

The example of dihydroxyl (alkyl) aryl alcohol can comprise: dihydroxy-benzene such as pyrocatechol; The methylbenzene diphenol; The ethylbenzene diphenol; Butylbenzene diphenol such as right-tert-butyl phenol; The dibutyl dihydroxy-benzene is as 4, and 6-is two-tert-butyl-Resorcinol; 4,4 '-thiobis (3-methyl-6-tert-butylphenol), 4,4 '-butylidene two (3-methyl-6-tert-butylphenol), 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 2,2 '-thiobis (phenol between 4-6-two-tert-butyl), 2,2 '-methylene radical-two (4-ethyl-6-tert-butyl phenol), 4,4 '-butylidene two (2,6-is two-tert-butyl phenol), 2,2 '-(3,5-pair-tert-butyl-4-hydroxyl) propane and 4,4 '-cycloethylene two (2,6-pair-tert-butyl phenol).

For the friction that strengthens between the DLC surface in contact reduces, dihydroxy alcohol is ethylene glycol, neopentyl alcohol, 1 preferably, 6-hexylene glycol, 2-methyl-2,4-pentanediol, 2-ethyl-2-methyl isophthalic acid, ammediol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1,11-undecane glycol or 1, the 12-dodecanediol.Can select to be not less than 300 high molecular hindered alcohols, preferably be not less than 400 high molecular hindered alcohols, as 2,6-pair-tert-butyl-4-(3,5-is two-uncle-4-(3,5-is two-tert-butyl-4-hydroxyphenyl) phenol alcohol because even under high temperature conditions such as engine, they have low volatility, fabulous thermal resistance and show the ability of the effect that friction reduces, and their ability can provide super oxidative stability.

Have three or more hydroxyl in three hydroxyls or its molecule of higher alcohol, be generally, preferably from three hydroxyl to six hydroxyl alcohol from three hydroxyl to ten hydroxyl alcohol.The example of these polyhydric alcohols can comprise: glycerol; Tri methylol alkane such as trimethylolethane, TriMethylolPropane(TMP) and tri hydroxy methyl butane; Tetrahydroxybutane; Season penta butanols; 1,2, the 4-trihydroxybutane; 1,3,5-penta triol; 1,2, the 6-hexanetriol; 1; Sorbyl alcohol; Adonitol; Arabitol; Xylitol; Mannitol; And their polymkeric substance or condenses.

The example of polymkeric substance or condenses can comprise: the dipolymer of glycerol arrives octamer as two glycerol, three glycerol and four glycerol; The dipolymer of TriMethylolPropane(TMP) to octamer as two TriMethylolPropane(TMP)s; The dipolymer of penta triol is to tetramer such as diamyl triol; Sorbose molecule inner injection compounds such as sorbyl alcohol-glycerol condensation product; Intramolecular condensation compounds or self condensation compound.

Also can use sugar as wood sugar, arabitol, ribose, rhamnosyl, glucose, fructose, seminose, sorbose, cellobiose, maltose, isomaltose, trehalose or sucrose as three hydroxyls or higher alcohol.

Three hydroxyls or higher alcohol can preferred three hydroxyl to six hydroxyl alcohol, as glycerol; Tri methylol alkane comprises trimethylolethane, TriMethylolPropane(TMP) and tri hydroxy methyl butane; Penta triol; 1,2, the 4-trihydroxybutane; 1,3,5-penta triol; 1,2, the 6-hexanetriol; 1; Sorbyl alcohol; Sorbitol ester; Sorbyl alcohol-glycerol condensation product; Adonitol; Arabitol; Xylitol or mannitol or their mixture.Wherein more preferably glycerol, tri methylol alkane, TriMethylolPropane(TMP), penta triol, sorbitol ester and their mixture, and oxygen level is no more than 20% polyhydric alcohol, preferably is no more than 30%, more preferably no more than 40%.In addition, higher than six hydroxyl alcohol polyhydric alcohol increases viscosity.

Carboxylic acid can be the compound with one or more carboxyls, as two or more mixture of aliphatics monocarboxylic acid, aliphatics polycarboxylic acid, carbocyclic ring carboxylic acid, heterocyclic carboxylic acid or its.

The monocarboxylic example of aliphatics can comprise: have the C1-C40 representative examples of saturated aliphatic monocarboxylic acid of a straight or branched saturated fatty base and have the C2-C40 unsaturated aliphatic monocarboxylic acid that has a straight or branched unsaturated aliphatic base of a unsaturated link(age) an optional position.

The monocarboxylic example of representative examples of saturated aliphatic can comprise: formic acid; Acetate (acetic acid); Propionic acid (n Propanoic acid); Butyric acid such as butanic acid and isopropylformic acid; Valeric acid such as positive valeric acid, isovaleric acid and hot valeric acid; Caproic acid such as n-caproic acid; Enanthic acid; Sad as n-caprylic acid; N-nonanoic acid such as pelargonic acid; Capric acid; Undecanoic acid; Dodecylic acid such as lauric acid; Tridecanoic acid; Tetradecanoic acid such as tetradecanoic acid; Pentadecylic acid; Hexadecanoic acid such as palmitinic acid; Margaric acid; Octadecanoic acid such as stearic acid; Nondecylic acid; Arachic acid; Heneicosanoic acid; Docosoic acid; Tricosanic acid; Lignoceric acid; Pentacosoic acid; Hexacosanoic acid; Carboceric acid; Octocosoic acid; Montanic acid and triacontanoic acid.

The monocarboxylic example of unsaturated aliphatic can comprise: vinylformic acid such as positive vinylformic acid; Propionic acid such as n Propanoic acid; Butenoic acid such as methylacrylic acid, Ba Dousuan and iso-crotonic acid; Pentenoic acid; Hexenoic acid; Heptenoic acid; Octylenic acid; Nonenoic acid; Decylenic acid; Undecylenic acid; Lauroleic acid; Tridecylenic acid; Tetradecenoic acid; Pentadecylenic acid; Gaidic acid; Heptadecenoic acid; Octadecenic acid such as oleic acid; Nonadecenoic acid; Eicosenoic acid; Two undecylenic acids; Docosenoic acid; Tricosenoic acid; Nervonic acid; Pentacosa alkene acid; Ximenic acid; Two heptadecenoic acids; Two octadecenic acids; Two nonadecenoic acids and lumequeic acid.

The example of aliphatics polycarboxylic acid can comprise: have a saturated or unsaturated aliphatic di-carboxylic acid of straight or branched C2-C40 saturated or the unsaturated fatty acids base, and the unsaturated fatty acids base has a unsaturated link(age) in an optional position; Saturated or unsaturated aliphatic tribasic carboxylic acid with the saturated or unsaturated aliphatic base of straight or branched, and the unsaturated fatty acids base has a unsaturated link(age) an optional position; Have a saturated or unsaturated aliphatic quaternary carboxylic acid of straight or branched C2-C40 saturated or the unsaturated fatty acids base, and the unsaturated fatty acids base there is a unsaturated link(age) in an optional position.

The example of aliphatic dicarboxylic acid can comprise: oxalic acid (oxalic acid); Propanedioic acid such as positive propanedioic acid; Succinic Acid such as succsinic acid and Methylpropanedioic acid; Pentanedioic acid such as L-glutamic acid and ethyl malonic acid; Hexanodioic acid such as adipic acid; Pimelic acid such as positive pimelic acid; Suberic acid such as positive suberic acid (spec acid); Nonane diacid such as lepargylic acid (azelaic acid); Sebacic acid such as positive sebacic acid (sebacic acid); The propylene diacid; Butene dioic acid such as toxilic acid and fumaric acid; Propene dicarboxylic acid such as citraconic acid and methylfumaric acid; Hexene diacid; Pentene dicarboxylic acid; Octene diacid; Nonene diacid and octene dicarboxylic acid.

The example of aliphatic tricarboxylic acids can comprise the third three acid, fourth three acid, penta 3 acid, oneself three acid, acid in heptan three, hot three acid, acid in the ninth of the ten Heavenly Stems three and acid in the last of the ten Heavenly stems three.

The carbocyclic ring carboxylic acid can be: have C3-C40 monobasic, binary, ternary or the quaternary carboxylic acid of a naphthalene nucleus, if wherein contain alkyl and thiazolinyl can be a straight or branched, and the position of two keys chooses wantonly, and substitution number and position are optional; Perhaps have C7-C40 monobasic, binary, ternary or quaternary carboxylic acid such as the C7-C40 aromatic series monocarboxylic acid of an aryl, if contain alkyl and thiazolinyl can be a straight or branched, position of double bond is selectable, and the number and the position that replace are selectable.

Example with monobasic, binary, ternary or quaternary carboxylic acid of a naphthalene nucleus can comprise: six ring monocarboxylic acids, methyl six ring monocarboxylic acids, ethyl six ring monocarboxylic acids, propyl group six ring monocarboxylic acids, butyl six ring monocarboxylic acids, amyl group six ring monocarboxylic acids, hexyl six ring monocarboxylic acids, seven ring monocarboxylic acids, eight ring monocarboxylic acid and trimethylammonium five rings dicarboxylic acid such as dextrocamphoric acids

Example with monobasic, binary, ternary or quaternary carboxylic acid of an aryl can comprise: benzene carboxylic acid (phenylformic acid); Methylbenzene carboxylic acid such as toluic acid; The ethylbenzene carboxylic acid; The propylbenzene carboxylic acid; Benzene dicarboxylic acid such as phthalic acid, isophthalic acid and terephthalic acid; Benzene tricarbonic acid such as trihemellitic acid; Benzene tertacarbonic acid such as pyromellitic acid; Naphthalene monocarboxylic acid such as naphthoic acid; Phenylpropionic acid such as hydratropic acid; Phenylacrylic acid such as atropic acid and styracin; Whitfield's ointment and alkyl salicylate with one or more C1-C30 alkyl.

Have one or more carboxyls in its molecule of heterocyclic carboxylic acid, as being C5-C40 heterocyclic carboxylic acid such as furancarboxylic acid, thio phenyl carboxylic acid, pyridine carboxylic acid comprise nicotinic acid and different nicotinic acid.

Ester is the oxygen-containing organic compound with one or more ester bonds, for example can be aliphatics monocarboxylic ester, aliphatics multi-carboxylate, carbocyclic ring carboxylicesters, heteroaromatic carboxylate or its one or more mixtures.Ester can be all hydroxyls or esterified complete ester of carboxyl in ester or the part ester that still leaves some hydroxyl or carboxyl.

The aliphatics monocarboxylic ester can be to be selected from monocarboxylic one or more compounds of above-mentioned aliphatics and the ester of one or more compound formation of selecting from above-mentioned monobasic, binary, trihydroxylic or higher alcohol.The preferred example of this ester can comprise glyceryl monooleate, glycerol dioleate, triolein, sorbitan monooleate and sorbitan dioleate.

Aliphatics multi-carboxylate can be one or more compounds of selecting from above-mentioned aliphatics polycarboxylic acid and from the ester of above-mentioned monobasic, binary, trihydroxylic or one or more compound formation of more selecting the higher alcohols.The preferred example of this ester can comprise: the diester of one or more polycarboxylic acids of selecting from the C4-C40 di-carboxylic acid, preferred C4-C18, more preferably C4-C12; And one or more compounds of from the single hydroxyl alcohol of C4-C40, selecting, preferred C4-C18, more preferably C6-C14 is as dibutyl maleinate, two tridecane penta diester, two-2-ethylhexyl adipic acid ester, diisodecyl adipate, the own diester of two tridecane or di 2 ethylhexyl sel; The multipolymer of this dibasic ester, as dibutyl maleinate and C4-C16 many-alpha-olefin; And the ester that alpha-olefin-diacetyl oxide addition produces and C1-C40 alcohol forms.

The carbocyclic ring carboxylicesters can be the ester of one or more compounds selected from above-mentioned carbocyclic ring carboxylic acid and one or more compound formation of selecting from above-mentioned monobasic, binary, trihydroxylic or higher alcohol.The preferred example of this ester can comprise aryl carboxylic acid such as phthalic acid ester, tritrimellitate, pyromellitic acid ester and salicylate.

Heteroaromatic carboxylate can be the ester of one or more compounds selected from above-mentioned heterocyclic carboxylic acid and one or more compound formation of selecting from above-mentioned monobasic, binary, trihydroxylic or higher alcohol.

Ether is the oxygen-containing organic compound with one or more ehter bonds, and, can be saturated or unsaturated aliphatic ether, aromatic oxide, cyclic ethers, poly-hydroxy alcohol ether and its two kinds or multiple mixture.

Example saturated or unsaturated aliphatic ether can comprise the saturated or unsaturated aliphatic ether of C1-C40, as dimethyl ether, Anaesthetie Ether, di ether, Di Iso Propyl Ether, dibutyl ether, diisobutyl ether, two n-pentyl ethers, hexyl ether, diheptyl ether, dicaprylyl ether, dinonyl ether, didecyl ether, dicaprylyl ether, two undecyl ethers, two lauryl ethers, double tridecyl ether, two myristyl ethers, two pentadecyl ethers, double hexadecyl ether, two heptadecyl ethers, two octadecyl ethers, two nonadecyl ethers, two eicosyl ethers, methyl ethyl ether, the ethyl n-propyl ether, methyl-isobutyl ether, methyl-tert-butyl ether, methyl n-pentyl ether, the methyl isoamyl ether, ethyl is to propyl ether, the ethyl isopropyl ether, the ethyl isobutyl ether, Ethyl Tertisry Butyl Ether, ethyl n-pentyl ether, the ethyl isoamyl ether, divinyl ether, hexadiene ether, ethylene methacrylic ether, methyl hexadiene ether, ethyl vinyl ether, ethyl hexadiene ether.But these saturated or unsaturated aliphatic ether straight or brancheds, and the position of unsaturated link(age) is optional.

The example of aromatic oxide can comprise methyl-phenoxide, phenyl ethyl ether, phenyl ether, dibenzyl ether, benzyl phenyl ether, α-Nai Ji ether, β-Nai Ji ether, polyphenylene oxide and perfluor ether.These compounds can have straight or branched, and representative examples of saturated aliphatic base or unsaturated link(age) are at the unsaturated aliphatic base of optional position and replace the position and number can be chosen wantonly.Preferred these compounds use with liquid state, and liquid state under the preferred room temperature.

The example of cyclic ethers can comprise C2-C40 cyclic ethers such as oxyethane, propylene oxide, trimethylene oxide, ring hydrogen furans, tetrahydropyrans, dioxane and glycidyl ether.These compounds can have a straight or branched, a carbocyclic ring of saturated or unsaturated aliphatic base or have a position saturated or unsaturated aliphatic base and unsaturated link(age) is optional carbocyclic ring, and the position of substitution and number are chosen wantonly.

The ether of polyhydroxy-alcohol can be one of ether of the ether of one or more polyhydroxy-alcohols of selecting from above-mentioned dihydroxyl, trihydroxy-or higher alcohol and one or more single hydroxyl alcohols of selecting from above-mentioned single hydroxyl alcohol.Ether can be complete ether, and wherein all hydroxyls are etherificates in the polyhydroxy-alcohol, and perhaps ether can be part ether, and wherein some hydroxyl remains complete.In order to obtain low friction characteristics, more preferably part ether.

Ketone is the oxygen-containing organic compound with one or more carbonyl keys, can be saturated or unsaturated aliphatic ketone, carbocyclic ring ketone, heterocyclic ketones, pure ketone, sour ketone or two or more mixture wherein.

Example saturated or the unsaturated aliphatic ketone can comprise the saturated or unsaturated aliphatic ketone of C1-C40, as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl Ketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), tert.-butyl methyl ketone, metacetone, butyrone, diisopropyl ketone, methyl vinyl ketone, mesityl oxide, espeleton.These compounds can have a straight or branched of saturated or unsaturated aliphatic base, and the position of unsaturated link(age) is chosen wantonly.

The example of carbocyclic ring ketone can comprise C1-C40 carbocyclic ring ketone, as cyclobutanone, cyclopentanone, pimelinketone, methyl phenyl ketone, Propiophenone, phenyl propyl ketone, benzene pentanone, benzophenone, dibenzyl ketone and 2-acetonaphthone.These compounds can have a straight or branched of saturated or unsaturated aliphatic base, and the position of unsaturated link(age) is optionally, and the position of substitution and number are optional.

The example of heterocyclic ketone can comprise the C1-C40 heterocyclic ketone, as thienylmethylketone and 2-acetofuran.These compounds can have a straight or branched of saturated or unsaturated aliphatic base, and the position of unsaturated link(age) is chosen wantonly, and alternative site and number are chosen wantonly.

The example of keto-alcohol can comprise the C1-C40 keto-alcohol, as hydroxyacetone, acetyl ethyl alcohol, Pyranton, phenacyl alcohol and bitter almond oil camphor.These compounds can have a carbocyclic ring or heterocycle, perhaps have the carbocyclic ring or the heterocycle of a straight or branched of saturated or unsaturated aliphatic base, and the position of unsaturated link(age) is chosen wantonly, and the position of substitution and number are chosen wantonly.

The example of ketone acid can comprise the C1-C40 ketone acid, as alpha-ketoacid, comprises pyruvic acid, benzoyl formic acid and phenyl-pyruvic acid; Beta-keto acid comprises etheric acid, propionyl acetate and benzoyl acetic acid; And γ-ketone acid, comprise levulinie acid and β-benzoyl propionyl acid.

Aldehyde is the oxygen-containing organic compound with one or more aldehyde radicals, can be saturated or unsaturated aliphatic aldehydes, carbocyclic ring aldehydes, heterocyclic aldehydes with and two or more mixture.

Example saturated or the unsaturated aliphatic aldehydes can comprise the saturated or unsaturated aliphatic aldehydes of C1-C40, as formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, isobutyric aldehyde, valeraldehyde, isovaleric aldehyde, pivalyl aldehyde, hexanal, aldehyde C-9, capraldehyde, undecyl aldehyde, dodecyl aldehyde, tridecyl aldehyde, myristate aldehyde, pentadecyl aldehyde, hexadecyl aldehyde, heptadecyl aldehyde, octadecyl aldehyde, propenal, crotonaldehyde, propynal, oxalic dialdehyde and suceinic aldehyde.These compounds can have a straight or branched of saturated or unsaturated aliphatic base, and the position of unsaturated link(age) is chosen wantonly.

The example of carbocyclic ring aldehyde can comprise C1-C40 carbocyclic ring aldehydes, as phenyl aldehyde, o-toluylaldehyde, a toluic aldehyde, p-tolualdehyde, salicylic aldehyde, phenylacrolein, α-naphthaldehyde and β-naphthaldehyde.These compounds can have a straight or branched of saturated or unsaturated aliphatic base, and the position of unsaturated link(age) is chosen wantonly, and the position of substitution and number are chosen wantonly.

The example of heterocyclic aldehydes can comprise C1-C40 heterocycle aldehydes, as furfural.These compounds can have a straight or branched of saturated or unsaturated aliphatic base, and the position of unsaturated link(age) is chosen wantonly, and the position of substitution and number are chosen wantonly.

Carbonate is the oxygen-containing organic compound with one or more carbonic acid keys, and can be to have a saturated or unsaturated C1-C40 fatty group, a carbocyclic ring, carbocyclic ring with a saturated or unsaturated aliphatic base or one have the saturated of carbocyclic ring or unsaturated aliphatic base, as dimethyl carbonate, diethyl carbonate, the dipropyl alkyl carbonate, di-isopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-t-butyl carbonate, diamyl carbonate, dihexyl carbonate, diheptyl carbonate, dioctyl carbonate, dinonyl carbonate, didecyl carbonate, two undecyl carbonate, two dodecyl carbonate, double tridecyl carbonate, two tetradecyl carbonate, two pentadecyl carbonate, double hexadecyl carbonate, two heptadecyl carbonate, two octadecyl carbonate, two phenyl carbons hydrochlorates.These compounds have a straight or branched of saturated or unsaturated fatty acids base, and the position of unsaturated link(age) is chosen wantonly, and the position of substitution and number are chosen wantonly.

In addition, also can use hydroxyl (many) alkylidene oxide carbonate, wherein alkylidene oxide is added on these carbonate.

Above-mentioned alcohol can represent that carboxylic acid represents with molecular formula R-(COOH) n with molecular formula R-(OH) n, ester is represented with molecular formula R-(COO-R ') n, ether is represented with molecular formula R-(O-R ') n, ketone is represented with molecular formula R-(CO-R ') n, aldehyde represents with molecular formula R-(CHO) n, and carbonate is represented with molecular formula R-(o-CooR ') n.

In the above-mentioned molecular formula R and R ' each all independently represent an alkyl, as alkyl, alkenyl, alkylidene group, cycloalkyl, aryl, alkaryl or aralkyl, or removed the alkyl of or heterogeneous hydrogen atom.Alkyl can have one or more groups or key, and it is selected from hydroxyl, carboxyl, carbonyl, ester bond or ehter bond, perhaps can also select to contain just like nitrogen, sulphur, heterogeneous ring compound, halogen such as fluorine or chlorine, phosphorus, boron, iron etc. except carbon, hydrogen, oxygen.

Charcoal number in the hydroxyl does not have particular determination, is preferably 1-40, more preferably 2-30, most preferably is 3-20.

The example of alkyl can comprise the C1-C40 alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, the straight or branched amyl group, the straight or branched heptyl, the straight or branched octyl group, the straight or branched nonyl, the straight or branched decyl, the straight or branched undecyl, the straight or branched dodecyl, the straight or branched tridecyl, the straight or branched tetradecyl, the straight or branched pentadecyl, the straight or branched hexadecyl, the straight or branched heptadecyl, the straight or branched octadecyl, the straight or branched nonadecyl, the straight or branched eicosyl, the straight or branched heneicosyl, the straight or branched docosyl, the straight or branched tricosyl, the straight or branched tetracosyl.Alkyl can a preferred C2-C30 alkyl, more preferably C3-C20 alkyl.

The example of thiazolinyl can comprise the C2-C40 thiazolinyl, as vinyl, the straight or branched propenyl, the straight or branched butenyl, the straight or branched pentenyl, the straight or branched hexenyl, the straight or branched heptenyl, the straight or branched octenyl, straight or branched nonene base, straight or branched decene base, straight or branched hendecene base, straight or branched laurylene base, straight or branched tridecylene base, straight or branched tetradecene base, straight or branched ten pentaene bases, straight or branched hexadecylene base, straight or branched 17 thiazolinyls, straight or branched octadecylene base, straight or branched 19 thiazolinyls, straight or branched icosa alkene base, straight or branched two hendecene bases, straight or branched docosene base, straight or branched tricosene base, straight or branched two tetradecene bases.Thiazolinyl is a C2-C30 thiazolinyl, more preferably C3-C20 thiazolinyl preferably.、

The example of cycloalkyl can comprise the C3-C40 cycloalkyl, as cyclopentyl, cyclohexyl, suberyl, ring octyl group.Cycloalkyl is the cycloalkyl of a C3-C20 preferably, more preferably the C5-C8 cycloalkyl.

The example of alkyl-cycloalk cyclic group can comprise the C4-C40 alkyl-cycloalkyl, as methylcyclopentyl, dimethylcyclopentyl, methylethyl cyclopentyl, diethyl cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, methylethyl cyclohexyl, diethyl cyclohexyl, methyl suberyl, dimethyl suberyl, methylethyl suberyl and diethyl suberyl.Alkyl-cycloalkyl is the alkyl-cycloalkyl of a C5-C20 preferably, more preferably C6-C12 alkyl-cycloalkyl, and comprise all possible Structural Isomerism thing.

The example of aryl can comprise the C6-C20 aryl, and as phenyl and naphthyl, more preferably aryl is a C6-C10 aryl.

The example of alkaryl can comprise: 1-substituted-phenyl such as tolyl, ethylphenyl, straight or branched propyl group phenyl, straight or branched propyl group phenyl, straight or branched propyl group phenyl, straight or branched propyl group phenyl, the straight or branched butyl phenyl, straight or branched amyl group phenyl, straight or branched hexyl phenyl, straight or branched heptyl phenyl, the straight or branched octyl phenyl, straight or branched nonyl phenyl, the straight or branched decyl phenyl, straight or branched undecyl phenyl, the straight or branched dodecylphenyl, the straight or branched tridecane; And have the aryl of two or more identical or different straight or branched aryl such as xylyl, diethyl phenyl, dipropyl phenyl, a 2-methyl-6-tert-butyl phenyl, 2,6-pair-tert-butyl-4-aminomethyl phenyl and 2,6-pair-tert-butyl-4-(3,5-pair-tert-butyl-4-benzyl) phenyl.Alkaryl can be selected the C7-C40 alkaryl, preferred C7-C20 alkaryl, more preferably C7-C12 alkaryl.Alkyl can select to have aryl, alkaryl or an aralkyl, and comprises all possible Structural Isomerism thing.

The example of aralkyl can comprise the C7-C40 aralkyl, as benzyl, phenylethyl, phenyl propyl, phenyl butyl, phenylpentyl and phenyl hexyl.It is the aralkyl of a C7-C20 that aralkyl can be selected, more preferably C7-C12 aralkyl, and comprise all possible Structural Isomerism thing.

Oxygen-containing organic compound also can above-claimed cpd derivative.This derivative can comprise it being the compound that a kind of and oxygen-containing organic compound reaction in nitrogenous compound, sulphur, sulfocompound, boron-containing compound, halogen, halogen compounds, metallic element, organic or inorganic containing metal compound and the alkylene oxide obtains at least, but is not limited to this.

For example, be selected from least above-mentioned alcohols, carboxylic-acid, ester class, ethers, ketone, aldehydes and in a kind of sulfuration of carbonate or halogenation as the compound of fluoridizing or chlorination obtains; At least a reaction product that is selected from above-mentioned group compound and sulfuric acid, nitric acid, boric acid or phosphoric acid, these sour esters or metal-salt; At least a above-mentioned group the compound and the alkylene oxide adduct of metal, containing metal compound or alkylene oxide reaction acquisition of being selected from; Perhaps can use at least a reaction product that is selected from above-mentioned group compound and amine compound.

Wherein, preferably be selected from least alcohols, carboxylic-acid, aldehydes with and a kind of compound of derivative and the reaction product of amine compound, as Mannich reaction products; At least be selected from the acroleic acid esterification product of above-mentioned group of a kind of compound; And the amides that is selected from a kind of compound of above-mentioned group at least.

Amine compound can be ammonia, monoamine, diamines or polyamines.The representation example of amine compound can comprise: ammonia; Alkylamine with a straight or branched C1-C30 alkyl is as methylamine, ethylamine, propyl group amine, butylamine, amylamine, hexyl amine, heptyl amine, octyl amine, nonyl amine, decyl amine, undecyl amine, lauryl amine, tridecyl base amine, tetradecylamine, pentadecyl amine, hexadecylamine, heptadecyl amine, octadecylamine, stearylamine, dimethyl amine, diethylamide, dipropylamine, dibutylamine, diamyl amine, dihexyl amine, diheptyl amine, dioctylamine, dinonyl amine, didecylamine, two undecyl amine, two lauryl amines, double tridecyl base amine, two tetradecylamines, two pentadecyl amine, double hexadecyl amine, two heptadecyl amine, dioctadecylamine, methylethyl amine, methyl-propyl amine, methyl butyl amine, ethyl propyl amine, N-Ethylbutylamine and propyl group butylamine; Alkenyl amine with a straight or branched C2-C30 alkenyl is as vinyl-amine, allylamine, butenylamine, octene amine and oleyl amine; Hydramine with a straight or branched C1-C30 alcohol radical is as carbinolamine, thanomin, Propanolamine, butanolamine, amylalcohol amine, hexanol amine, octanol amine, enanthol amine, nonyl alcohol amine, methanol amine, methyl alcohol Propanolamine, methyl alcohol butanolamine, ethanol propanol amine, ethanol and butanol amine and propyl alcohol butanolamine; Straight or branched C1-C30 alkylidene group diamine is as methylene radical diamine, ethylidene diamine, propylidene diamine and butylidene diamine; Polyamines such as diethylenetriamine, triethylene tetramine, TEPA tetraethylene pentamine and penta ethene hexamine; Above-mentioned monoamine, diamines, polyamines with a C8-C20 alkyl or alkenyl are as undecyl diethylamide, dodecyl diethanolamine, dodecyl dipropanolamine, oil base diethanolamine, oil base trimethylene diamine and stearyl butylidene amylamine; Heterogeneous ring compound such as N-hydroxyethyl oil-based imidazoline; The alkylene oxide adduct of these compounds; With and composition thereof.

Wherein preferred these nitrogen compounds, have C10-C20 alkyl, the alkylamine of straight or branched, as decyl amine, lauryl amine, tridecyl amine, heptadecyl amine, octadecylamine, oil base amine and stearic amine.

Oxygen-containing organic compound was discussed.In order to provide superior friction to reduce effect, in listed compound, preferably has the compound of a hydroxyl.In addition, still for providing superior friction to reduce effect, alcohol radical more can be directly connected on the carbonyl, as carboxyl than hydroxyl.The number of this hydroxyl in compound do not have particular determination, but for superior friction reduces effect, preferred compound has hydroxyl as much as possible.But, when this compound uses with a kind of medium such as lubricant base oil, consider, can limit the number of hydroxyl for solubility.

Fatty amine can be those compounds with straight or branched C6-C30 aliphatic alkyl, preferred C8-C24, more preferably C10-C20 aliphatic alkyl.If outside scope 6-30, can not obtaining enough frictions, carbon atom number do not reduce effect.As long as the straight or branched aliphatic alkyl that is comprised can select to comprise other alkyl in above-mentioned scope.

The example of straight or branched C6-C30 aliphatic alkyl can comprise: alkyl, as hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, ceryl, heptacosyl, octacosyl, nonacosyl and triacontyl; And thiazolinyl, as hexenyl, heptenyl, octenyl, nonene base, decene base, hendecene base, laurylene base, tridecylene base, tetradecene base, ten pentaene bases, hexadecylene base, 17 thiazolinyls, octadecylene base, 19 thiazolinyls, icosa alkene base, two hendecene bases, docosene base, tricosene base, two tetradecene bases, pentacosa alkene base, cerotene base, 27 thiazolinyls, two octadecylene bases, 29 thiazolinyls and 30 thiazolinyls.

Abovementioned alkyl or thiazolinyl can be straight or brancheds, and the two keys in the thiazolinyl can be at an arbitrary position.

Aliphatic amide can be various amine compound, as monoamine, polyamines class, alcamines, perhaps has the tetrahydroglyoxaline of above-mentioned straight or branched C6-C30 aliphatic group, perhaps its derivative.

The example of monoamine can comprise lauryl amine, bay diethylamide, palmitamide, stearylamine and oleyl amine.

The example of polyamines can comprise stearyl tetren and oil base trimethylene diamine.

The example of hydramine can comprise lauryl diethanolamine, dodecyl dipropanolamine and oil base diethanolamine.

The example of nitrogen-containing heterocycle compound can comprise N-hydroxyethyl oil-based imidazoline.

Derivative can be alkylene oxide adduct, sour modified compound etc.

The alkylene oxide adduct can be by a nitrogen-atoms in the above-mentioned various amine compound being carried out the compound that the alkylene oxide addition reaction obtains.The example of this alkylene oxide adduct can comprise that an elementary monoamine with C6-C28 alkyl or alkenyl is carried out alkyl oxidation addition reaction obtains N, N-two polyoxyalkylenes-N-alkyl-or alkenyl amine, preferred especially N, N-two polyoxyalkylenes-N-oil base amine.

The acid modified compound can preferably be used the aliphatics monocarboxylic acid, especially C2-C30 aliphatics monocarboxylic acid by obtaining with above-mentioned carboxylic acid and above-mentioned various amine reaction; Above-mentioned aliphatics polycarboxylic acid, especially C2-C30 aliphatics polycarboxylic acid comprises oxalic acid; Perhaps above-mentioned carbocyclic ring carboxylic acid, especially C6-C30 carbocyclic ring carboxylic acid comprise lipid acid, trihemellitic acid; Perhaps pyromellitic acid is so that neutralization or amidation amino and/or imino-wholly or in part.

Reduce effect in order further to improve friction, lubricant of the present invention can select to contain a kind of required friction modifier.If contain the friction modifier, its content does not have particular determination, by being no more than 3.0% of lubricant total amount quality, is preferably the 0.05-3.0% of total amount quality, and the 0.1-2.0% of total amount quality more preferably most preferably is the 0.5-1.4% of total amount quality.

Except said components, lubricant of the present invention is according to the performance needs, can select to comprise other additive, this additive is selected from viscosity index improver, pour point reducer, antiwear agents, extreme pressure additive, the friction modifier except that above-mentioned, the metal brightener except that component (B), no ash content dispersion agent, the antioxidant except that component (D), rust inhibitor, metal inactivator, tensio-active agent, demulsifying compound, sealing swelling agent, froth suppressor, staining agent and composition thereof.

Viscosity index improver can be a kind of so-called non-dispersive formulation viscosity index improver, as a kind of polymkeric substance or a kind of its hydrogenated products of various methacrylic acids, or a kind of its multipolymer of any bonded and a kind of its hydrogenated products; Or a kind of so-called formulation viscosity index improver that disperses also comprises and the compound with various methacrylic ester copolymerizationization of nitrogen.Also can use the non-dispersive formulation or disperse formulation ethene-α-hydrocarbon copolymer with and the hydrogenated products of hydride, polyisobutene and its hydrogenated products, vinylbenzene-diene copolymers, styrene-maleic anhydride copolymer, polyoxyethylene alkylphenyl ethene etc.α-hydrocarbon is propylene, 1-butylene or 1-amylene preferably.

The molecular weight of viscosity index improver should be selected under low shear stability.The molar mass average of this viscosity index improver is counted representation example: dispersion agent or non-dispersive formulation polymethyl are 5000-1000000, are preferably 100000-800000; Polyisobutylene or its hydride are generally 800-5000; Ethene-α-hydrocarbon copolymer with and hydride be generally 800-300000, be preferably 10000-200000.Can use a kind of composition of one or more viscosity index improvers, preferred content is generally the 0.1-40.0% of lubricant total amount.

Wherein, in order to keep low friction characteristics, preferred especially polymethacrylate viscosity index improver.

Pour point reducer can be the pour point reducer that is suitable for the lubricant base oil.For example can use polymethacrylate base pour point reducer.

Known antiwear agents and extreme pressure additive that antiwear agents and extreme pressure additive use in can lubricant.Its example can comprise: phosphate cpd such as phosphite, phosphoric acid salt, thiophosphorous acid salt, thiophosphate, dithiophosphates, its metal-salt such as its zinc salt or its amine salt; And the sulfur-bearing extreme pressure additive, as the sulfuration oils and fats, sulfuration ester class, hydrocarbon is sulfide-based and dithiocarbamate(s).As antiwear agents, preferably there is not the phosphoric acid antiwear agents of sulphur, because its ability that has acquisition or keep low friction characteristics.Also preferred dithiocarbamate(s) antiwear agents is because it has the ability of the low friction characteristics of fabulous maintenance.

In the lubricant of the present invention, if contain antiwear agents and/or extreme pressure additive, its content is not particularly limited, and is generally the 0.1-5 quality % of lubricant total amount.When especially using the phosphoric acid antiwear agents, its content is not particularly limited, and phosphoric accounts for the 0.01-0.1 quality % of total composition usually, preferably is no more than 0.08 quality %, more preferably no more than 0.06 quality %.When using the sulfur-bearing antiwear agents, its content is not particularly limited, and preferred element sulphur is no more than 0.15 quality % of total composition, more preferably no more than 0.1 quality %, is most preferably not exceeding 0.05 quality %.The antiwear agents that does not especially preferably contain sulfur-bearing.

Other friction modifier can be for example dithiocarbonic acid molybdenum, molybdenum dithiophosphate or dithio molybdenum trisulfate.

No ash content dispersion agent can be a kind of known dispersion agent that uses in the lubricant.Preferred example can comprise poly-butyl fourth diester dispersion agent, poly-butyl benzylamine dispersion agent, poly-butylamine dispersion agent and Mannich dispersant, and wherein preferably poly-butyl molecular-weight average number is 700-3500, more preferably 900-2500.No ash content dispersion agent also can be boron compound derivative, carboxylic acid derivative etc.

If contain no ash content dispersion agent, its content is not particularly limited, and is generally the 0.1-15 quality % of lubricant total amount.

Antioxidant except component (D) can be a kind of known antioxidant that uses in the lubricant.Preferred example can comprise the metal matrix antioxidant, as molybdenum base antioxidant and copper base antioxidant.

If contain antioxidant, its content is not particularly limited in lubricant of the present invention, is generally the 0.01-3 quality % of lubricant total amount.

When in lubricant of the present invention, comprising antioxidant, preferred this antioxidant is a kind of molybdenum base antioxidant, as molybdenum dithiocarbamate, molybdenum dithiophosphate, a kind of molybdenum amine complex or a kind of molybdenum-succinyl title complex, particularly molybdenum dithiocarbamate.The content of molybdenum base antioxidant is the 0.001-0.1 quality % that molybdenum element accounts for the lubricant total amount, preferably is no more than 0.03 quality %, more preferably no more than 0.02 quality %.

Rust inhibitor can be for example alkylbenzene sulfonate, dinonylnaphthalene sulfonic acid salt, alkenyl succinate or poly-hydroxyl alcohol ester.

Demulsifying compound can be for example a kind of macrogol base nonionogenic tenside, as Voranol EP 2001, polyoxyethylene alkyl phenyl ether or polyxyethylated naphthyl ether.

Metal deactivators can be for example tetrahydroglyoxaline, a kind of pyrimidine derivatives, benzotriazole or thio biphosphole.

Froth suppressor can be for example silicon, fluorine silicon or fluoro-alkyl ether.

In lubricant of the present invention, if contain rust inhibitor and/or demulsifying compound, its content is not particularly limited, and is generally the 0.01-5 quality % of lubricant total amount.If contain metal deactivators, its content is not particularly limited, and can suitably select common scope is the 0.0005-1 quality % of lubricant total amount.

Select in the additive above-mentioned, zinc dithiophosphate and sulfur-bearing metal brightener are as all suppressing the acquisition or the maintenance of low friction between the DLC surface in contact with sulfur-crosslinked alkaline earth metal sulfonate and alkaline earth phenolates.Therefore, in fact preferably do not contain these compositions.Because of same reason, be selected from the above-mentioned additive, contain sulfur-containing additive as much as possible less, in fact more preferably do not contain sulfur-containing additive.In addition, the thinner that comprises in the additive is preferably has the low total aromatic content and the material of low sulfur content, does not more preferably in fact have the material of aromatics and sulphur content.

Based on above-mentioned consideration, sulphur content in the lubricant of the present invention preferably is no more than 0.2% of quality, more preferably no more than 0.1% of quality, preferably is no more than 0.05% of quality again, especially preferably be no more than 0.01% of quality, more especially preferably be no more than 0.005% of quality.Preferably in fact there is not sulphur in the lubricant.

In system of the present invention, adopt the mode that is suitable for this system type, as sealing means or circulating current system, by lubricant of the present invention is provided between surface in contact, lubricant of the present invention can be dispersed between the surface in contact, and move this system.

System of the present invention has relatively movably, be coated with one of at least the face-to-face surface in contact of DLC, for example, can be oil engine as four-or two-cycle engine, especially air valve structure class, piston type, piston lopps, piston skirt class, steam jacket class, connecting rod class, crankshaft type, bearing class, roller bearing class, metal gear class, chain class, band class, oil pump etc.Also comprise the driving mechanism class and other systems that has the various work surface in contacts under serious friction condition and need low friction characteristics that drive transmit machine such as gear class, have the hard disk drive contact surface.

In system of the present invention, air valve structure example in the preferred oil engine can comprise the air valve structure with surface in contact, this surface in contact is formed that the disc type of making by forming the DLC film on the steel matrix is thin fills up or the lifting top surface, and the cam lobe of being made by a kind of low-alloy cold hard cast-iron, converted steel or heat refining carbon steel or a kind of material of any bonded of these materials.

In fact the method that the DLC surface in contact is lubricated according to the present invention can be between the above-mentioned face-to-face surface in contact that applies with DLC relatively movably, one of at least, with lubricant of the present invention it is lubricated.By lubricating this DLC coated surface with lubricant of the present invention, can the low friction characteristics that keep the DLC surface in contact steady in a long-term.

Embodiment

Below with reference to embodiment and comparing embodiment, be explained in more detail the present invention, but the present invention is not limited to this embodiment, and the present invention can adopt variety of way to modify or improvement.

Embodiment 1-1 to 1-2 and comparing embodiment 1-1 to 1-2

Surface in contact embodiment as in the low friction motor system has prepared the testpieces with the OPTIMOLINSTRUMENT manufacturing, is used for the SRV friction testing machine.One SUJ2 heat treatment material is polished into a plate-like material and a columnar material, and, with the looping band these materials are polished and to become to have predetermined surface rugosity (Ra=0.2um or lower), prepared this testpieces.Adopt VCD to handle, applied the plate-like material surface that is obtained, make it have pre-determined thickness shown in the voting 1 with a-C (invisible carbon) type DLC, and, predetermined surface rugosity (Ra=0.1um or lower) polished into the looping band.Fig. 1 represents the testpieces that obtained, and its data is listed in the table 1.

Among Fig. 1, label 10 indicating panels, label 11 expression posts, arrow are represented to use downward pressure and the horizontal slip campaign of post 11 on dish 10 in the functional inspection of subsequent discussion.

Table 1

Matrix

DLC films

Film thickness (um)

Surface hardness Hv

Surface roughness Ra (um)

Dish	The SUJ2 heat treatment material	a-C	1.1	1800	0.04
						Post	The SUJ2 heat treatment material	Do not have		750	0.05

The preparation of lubricant

The comparison that table 2 expression is done according to lubricant and comparing embodiment 1-1 and the 1-2 of embodiments of the invention 1-1 and 1-2.The lubricant that is obtained has following functional inspection.The result is illustrated in the table 2.

In table 2, base oil I be a kind of when having 100 ℃ kinetic viscosity be that 24.0mm2/s, viscosity index are 125, total aromatic content accounts for quality 1.0%, sulphur content is the serious hydrocracking mineral oil of quality 0.001%.Base oil II is a kind of many α hydroxyl oil (SHF41 is made by EXXON-MOBIL CHEMICAL), does not have aromatics and sulphur compound in fact, and kinetic viscosity is 3.9mm2/s when having 100 ℃, and viscosity index is 123.Base oil III is a kind of solvent dewaxing mineral oil, and kinetic viscosity is 4.4mm2/s when having 100 ℃, and viscosity index is 102, and total aromatics amount is 21.0% of a quality, and sulfur content is 0.60% of a quality.The additive bag is that a kind of SG is grade packaged, comprises zinc dithiophosphate, calcium sulfate etc.It is 0.35% of quality that the lubricant of comparing embodiment 1-2 has total sulfur.

Functional inspection

The experimental piece of above-mentioned preparation is placed on the OPTIMOL SRV experimental machine, every kind shown in the table 2 lubricant is dropped on the experimental piece, and measured coefficient of friction after under the following condition ten minutes and 30 minutes.The result is illustrated in the table 2.

Initial coefficient of friction after coefficient of friction after ten minutes is represented to stablize, the coefficient of friction after 30 minutes is represented the coefficient of friction in the state, wherein is formed with lubricant film on surface in contact, perhaps lubricant can carry out oxidation degeneration or reaction.Can estimate initial friction characteristics and retentivity thereof at short notice by this experiment.

Experiment condition

Temperature: 80 ℃; Load: 400N; Amplitude: 3mm; Frequency: 50Hz.

Table 2

The lubricant of embodiment demonstrates extremely low coefficient of friction after 10 minutes as can be seen from Table 2, even does not also observe the coefficient of friction increase after 30 minutes, shows the stable low friction characteristics that keeps.The lubricant essence of embodiment 1-1 of comparing is made up of the lubricating base oil outside the scope of the invention, the lubricant of comparing embodiment 1-2 contains a kind of lubricating base oil in the scope of the invention, and additive comprises zinc dithiophosphate and sulfuration stain remover, show high coefficient of friction after 10 minutes, can be observed coefficient of friction after 30 minutes significantly increases expression and does not keep friction characteristics.

Embodiment 2-1 to 2-3, reference example 2-1 and comparing embodiment 2-1

The lubricant composition preparation

Be shown in the table 3 according to the lubricant of embodiment of the invention 2-1 to 2-3 and the lubricant comparison sheet of reference example 2-1 and comparing embodiment 2-2.The lubricant that obtains is carried out following demonstration experiment, use experimental piece and system class to be similar to experimental piece and system used among table 1 and the 1-1 embodiment illustrated in fig. 1.The result is illustrated in the table 3.

In table 3, identical in base oil I and the table 2.No sulfur metal stain remover is a kind of peralkaline calcium salicylate, contains lime carbonate, and having the base number is 166mgKOH/g, and calcium contents is 6.2% of a quality; No sulfur metal stain remover II is that a kind of mistake that contains lime carbonate subtracts basic calcium salicylate, and having the total alkali radix is 170mgKOH/g, and calcium contents is 6.8% of a quality; The sulfur-bearing metal brightener is a kind of alkalization calcium sulfate of crossing calciferous, and having the total alkali radix is 320mgKOH/g, and calcium contents is 12.5% of a quality, and sulphur content is 2% of a quality.Friction modifier I is a glycerine list grease.Additive bag I comprises the dialkyl group zinc phosphate, viscosity index improver, antioxidant, dispersion agent etc.; Additive bag II is that a kind of SG that contains zinc dithiophosphate and calcium sulfate is grade packaged.

Show that experiment (1) SRV friction experiment adopts and embodiment 1-1 same way as is carried out, but do not use the lubricant shown in the table 3, the result is illustrated in the table 3.

(2) running of an engine friction experiment

The running of an engine friction experiment carries out under following condition, and an ordinary steel pad and a DLC are coated with film gasket, uses as pad of engine, and this coated gasket has above-mentioned same film thickness, surface hardness and surface roughness.Based on the friction torque that the lubricant of ordinary steel pad and comparing embodiment 2-1 obtains, the lubricant of embodiment 2-3 is measured friction change.The result is illustrated in the table 3.In addition, utilize SRV friction testing machine comparative experiments chamber to estimate, running of an engine friction test can be estimated the energy conservation characteristic of whole engine.

Test conditions

A: in the time of oily warm 100 ℃, motor speed is 800rpm

B: in the time of oily warm 60 ℃, motor speed is 2000rpm

(3) low friction characteristics keeps functional inspection

" 4. the internal combustion engine lubrication oil-proofness is determined (ISOT) " according to " lubricating oil-oxidative stability is determined " part among the JIS K2154 comes every kind of lubricant of oxidation.After the inspection, every kind of thickened oil is carried out above-mentioned SRV friction test, measure coefficient of friction after 30 minutes.This test objective is to keep operation for the low friction characteristics of detailed assessment.

Table 3

As can be seen from Table 3, the lubricant of embodiment 2-1 to 2-3 contains a kind of metal brightener that does not have sulphur, shows utmost point low frictional factor after 10 minutes, even does not observe the coefficient of friction increase after 30 minutes, the low friction characteristics of the stable maintenance of expression.

On the contrary, the lubricant of comparing embodiment 2-1 contains zinc dithiophosphate and a kind of calcium sulfate stain remover, is all showing high coefficient of friction after 10 minutes He after 30 minutes, can not keep coefficient of friction well.The lubricant of reference example 2-1 contains sulfur-bearing metal brightener and glycerine list grease, shows enough low coefficient of friction, increases but observe coefficient of friction after 30 minutes, shows to keep low friction characteristics well.

Compare with the friction torque that lubricant obtains of comparing embodiment 2-1 with the ordinary steel pad, when using DLC to be coated with film gasket and to contain the lubricant of a kind of embodiment 2-3 that does not have a sulfur metal stain remover, obtained extremely superior friction torque reduced rate, be to be about 19% under high temperature, the slow speed of revolution condition, be about 7% under low temperature, the high speed conditions.

Embodiment 3-1 to 3-2, reference example 3-1 and comparing embodiment 3-1

The preparation of lubricant composition

Table 4 expression is compared according to the lubricant of embodiments of the invention 3-1 to 3-2 and the lubricant preparation of reference example 3-1 and comparing embodiment 3-1.The lubricant that obtains is checked: (1) check with the SRV friction of embodiment 2-1 the same manner, use with table 1 and 1-1 embodiment illustrated in fig. 1 in used similar testpieces and system; (2) the running of an engine friction is checked; (3) low friction characteristics keeps functional inspection.The result is illustrated in the table 4.

In table 4, identical in base oil I and the table 2.No sulphur phosphate cpd is the dialkyl group zinc phosphate, and wherein alkyl is a butyl, and to contain quality be 7.5% phosphorus and a kind of thinner.It is 7.2% of quality that dialkyl group two zinc dithiophosphates have phosphorus content, and secondary/elementary ratio is 65/35 (phosphorus mass content).Additive bag I contains a kind of lime carbonate iron that contains and crosses base calcium salicylate, a kind of viscosity index improver, a kind of antioxidant (ashless somatotype and be MoDCT), a kind of dispersion agent etc.Identical in friction modifier I and additive bag II and the table 3.

Table 4

	Embodiment 3-1	Reference example 3-1	Embodiment 3-2	Comparing embodiment 3-1
					Base oil (% of base oil total amount quality) base oil I (lubricating base oil (A))	100	100	100	100
Additive (% of component total amount quality) is no sulphur phosphate cpd zinc dialkyl dithiophosphate friction modifier I (C)	1.0 - 1.0	- 1.1 1.0	1.0 - 1.0	- - -
					Additive-package I additive-package II	- -	- -	14.2 -	- 13.6
Functional inspection result (1) the SRV inspection that rubs: after 10 minutes: 60 ℃ of (3) low friction characteristics maintenances of 100 ℃ of 2000rmp of (2) running of an engine friction inspections-pad (friction torque reduced rate %) 800rmp functional inspection after 30 minutes	0.038 0.040 - - 0.056	0.062 0.095 - - -	0.045 0.045 a-C 19.0 8.0 -	0.082 0.095 steel 0 (std) 0 (std)-

As can be seen from Table 4, the lubricant of embodiment 3-1 to 3-2 contains a kind of phosphate cpd that does not have sulphur, shows utmost point low frictional factor after 10 minutes, even does not observe the coefficient of friction increase after 30 minutes, the low friction characteristics of the stable maintenance of expression.

On the contrary, the lubricant of comparing embodiment 3-1 contains zinc dithiophosphate and a kind of calcium sulfate stain remover, is all showing high coefficient of friction after 10 minutes He after 30 minutes, can not keep coefficient of friction well.The lubricant of reference example 3-1 contains zinc dithiophosphate and glycerine list grease, shows enough low coefficient of friction, increases but observe coefficient of friction after 30 minutes, shows to keep low friction characteristics well.In addition, the lubricant of embodiment 3-2 contain as a kind of no ash content antioxidant of antioxidant and a kind of contain the molybdenum antioxidant (MoDTC content: molybdenum account for constituent mass 0.02%) composition.Proof MoDTC does not resemble zinc dithiophosphate, keeps operation not have negatively influencing to low friction.

Compare with the friction torque that lubricant obtains of comparing embodiment 1 with the ordinary steel pad, when using DLC to be coated with film gasket and to contain the lubricant composition of a kind of embodiment 2 that does not have a sulphur phosphate cpd, obtained extremely superior friction torque reduced rate, be to be about 19% under high temperature, the slow speed of revolution condition, be about 8% under low temperature, the high speed conditions.

Embodiment 4-1 to 4-2 and comparing embodiment 4-1

The preparation of lubricant composition

Table 4 expression is compared according to the lubricant of embodiments of the invention 4-1 to 4-2 and the lubricant preparation of comparing embodiment 4-1.The lubricant that obtains is checked: (1) check with the SRV friction of embodiment 1-1 the same manner, use with table 1 and 1-1 embodiment illustrated in fig. 1 in used similar testpieces and system; (3) low friction characteristics keeps functional inspection.The result is illustrated in the table 5.

In table 5, identical in base oil I and the table 2.No sulphur antioxidant is octyl group-3-(3,5-couple-tert-butyl-4-hydroxybenzene) propionic ester, is alkyl diphenyl base amine and there is not sulphur antioxidant I I.Friction modifier I is a glycerine list grease.

Table 5

As can be seen from Table 5, the lubricant of embodiment 4-1 to 4-2 contains a kind of no sulphur does not have the ash content antioxidant, shows utmost point low frictional factor after 10 minutes, even does not observe the coefficient of friction increase after 30 minutes, the low friction characteristics of the stable maintenance of expression.

On the contrary, the lubricant of comparing embodiment 4-1 contains sulfur-bearing does not have the ash content antioxidant, shows high coefficient of friction after 10 minutes, and observing coefficient of friction after 30 minutes increases.

Embodiment 5-1 to 5-7

The lubricant composition preparation

Table 6 expression is according to the lubricated preparation of embodiments of the invention 5-1 to 5-7.The lubricant that obtains is checked: (1) check with the SRV friction of embodiment 1-1 the same manner, use with table 1 and 1-1 embodiment illustrated in fig. 1 in used similar testpieces and system; (3) low friction characteristics keeps functional inspection same way as with embodiment 2-1.The result is illustrated in the table 6.

In table 6, base oil I and various additives and table 2 to 5 identical.

To 5, as can be seen from Table 6, in fact, component (B) does not influence the friction characteristics of green oil to the interpolation of (D) based on table 3.But, compare with green oil, behind ISOT to the friction inspection of oxidation (degeneration) oil, this is to improve the typical test mode that lubricant oxidation is degenerated, and proves that coefficient of friction significantly increases, yet, the interpolation of component (B) to (D) suppresses this increase, and improves the maintenance operation of low friction characteristics.

Claims (9)

1. system with diamond-like carbon (DLC) surface in contact comprises:

Relatively movably, be coated with one of at least DLC face-to-face surface in contact and

Be used to have a kind of lubricant of DLC surface in contact system, this lubricant is dispersed between the described contact surface; Described lubricant meets the following conditions (a) and (b):

(a) the described lubricant that is used to have DLC surface in contact system comprises a kind of lubricating base oil (A), and this lubricating base oil (A) contains the base oil (X) of 70-100 quality % as principal constituent; This base oil (X) is formed and is comprised the mineral oil of at least a hydrocracking, the isomerized mineral oil of a kind of wax and a kind of many α thiazolinyl oil; Kinetic viscosity was 2-20mm when wherein said base oil (X) had 100 ℃ ²/ s, total aromatic content is not higher than 5 quality %, and sulphur content is not higher than 0.005 quality %; With

(b) the wherein said lubricant that is used to have DLC surface in contact system has sulphur content and is not higher than 0.2 quality %.

2. according to the system of claim 1, it is characterized in that, the described lubricant that is used to have DLC surface in contact system also comprises at least a no sulfur metal stain remover (B), a kind of phosphorus compound (C) and ashless antioxidant of a kind of no sulphur (D) that does not have sulphur, wherein, the metallic element of no sulfur metal stain remover (B) is the 0.01-1 quality % of lubricant total amount, the phosphoric of the phosphorus compound of no sulphur (C) is the 0.01-0.1 quality % of lubricant total amount, the ashless antioxidant of no sulphur (D) is the 0.01-5 quality % of lubricant total amount, and the surplus of lubricant is lubricating base oil (A).

3. according to the system of claim 1, it is characterized in that, the described lubricant that is used to have DLC surface in contact system also comprises a kind of friction modifier, this modifier is formed and is comprised a kind of oxygen containing organic compound and fatty amine at least, wherein, the friction modifier is the 0.05-3.0 quality % of lubricant total amount.

4. according to the system of claim 1, it is characterized in that described surface in contact comprises the surface in contact in the oil engine.

5. the method for a lubricated DLC surface in contact comprises a kind of lubricant that is used to have DLC surface in contact system, and this lubricant is dispersed between the described contact surface, the lubricated face-to-face surface in contact that is coated with DLC relatively movably, one of at least; Described lubricant meets the following conditions (a) and (b):

(a) the described lubricant that is used to have DLC surface in contact system comprises a kind of lubricating base oil (A), and this lubricating base oil (A) contains the base oil (X) of 70-100 quality % as principal constituent; This base oil (X) is formed and is comprised the mineral oil of at least a hydrocracking, the isomerized mineral oil of a kind of wax and a kind of many α thiazolinyl oil; Kinetic viscosity was 2-20mm when wherein said base oil (X) had 100 ℃ ²/ s, total aromatic content is not higher than 5 quality %, and sulphur content is not higher than 0.005 quality %; With

(b) the wherein said lubricant that is used to have DLC surface in contact system has sulphur content and is not higher than 0.2 quality %.

6. lubricant that is used to have (DLC) surface in contact system, described lubricant is lubricated relatively movably, be coated with one of at least the face-to-face surface in contact of DLC; Described lubricant meets the following conditions (a) and (b):

(a) the described lubricant that is used to have DLC surface in contact system comprises a kind of lubricating base oil (A), and this lubricating base oil (A) contains the base oil (X) of 70-100 quality % as principal constituent; This base oil (X) is formed and is comprised the mineral oil of at least a hydrocracking, the isomerized mineral oil of a kind of wax and a kind of many α thiazolinyl oil; Kinetic viscosity was 2-20mm when wherein said base oil (X) had 100 ℃ ²/ s, total aromatic content is not higher than 5 quality %, and sulphur content is not higher than 0.005 quality %; With

(b) the wherein said lubricant that is used to have DLC surface in contact system has sulphur content and is not higher than 0.2 quality %.

7. according to the lubricant of claim 6, also comprise at least a no sulfur metal stain remover (B), a kind of phosphorus compound (C) and ashless antioxidant of a kind of no sulphur (D) that does not have sulphur, wherein, the metallic element of no sulfur metal stain remover (B) is the 0.01-1 quality % of lubricant total amount, the phosphoric of the phosphorus compound of no sulphur (C) is the 0.01-0.1 quality % of lubricant total amount, the ashless antioxidant of no sulphur (D) is the 0.01-5 quality % of lubricant total amount, and the surplus of lubricant is lubricating base oil (A).

8. according to the lubricant of claim 6, also comprise a kind of friction modifier, this modifier is formed and is comprised a kind of oxygen containing organic compound and fatty amine at least, and wherein, the friction modifier is the 0.05-3.0 quality % of lubricant total amount.

9. according to the lubricant of claim 6, it is characterized in that described lubricant is not selected from the sulfur-containing additive of zinc dithiophosphate, sulfur-bearing metal brightener and composition thereof.